Selective production of linear triethylenetetramine and aminoethylethanolamine

ABSTRACT

This invention relates to a process for making amines having a high yield weight percent of linear triethylenetetramine (L-TETA) and aminoethylethanolamine (AEEA) by condensing an amino compound in the presence of a condensation catalyst selected from a Group IVB metal oxide, a Group VIB metal-containing substance and a promoted condensation catalyst. This invention also relates to an alkyleneamines producers composition rich in L-TETA and AEEA.

RELATED APPLICATIONS

The following are related, commonly assigned applications, filed on aneven date herewith: U.S. patent application Ser. No. 501,917; U.S.patent application Ser. No. 501,919; U.S. patent application Ser. No.501,906; U.S. patent application Ser. No. 501,903; U.S. patentapplication Ser. No. 501,998; U.S. patent application Ser. No. 501,826;and U.S. patent application Ser. No. 501,920; all incorporated herein byreference.

The following are related, commonly assigned applications: U.S. patentapplication Ser. No. 07/136,615, filed Dec. 22, 1987 now abandoned; U.S.patent application Ser. No. 07/390,829, filed Aug. 8, 1989; U.S. patentapplication Ser. No. 07/390,706, filed Aug. 8, 1989; U.S. patentapplication Ser. No. 07/390,709, filed Aug. 8, 1989 (now U.S. Pat. No.4,983,736); U.S. patent application Ser. No. 07/390,828, filed Aug. 8,1989; U.S. patent application Ser. No. 07/390,708, filed Aug. 8, 1989(now abandoned in favor of continuation Ser. No. 07/742,731, filed Aug.16, 1991, which in turn has been abandoned in favor of continuation Ser.No. 934,901, filed Aug. 26, 1992) and U.S. patent application Ser. No.07/390,714, filed Aug. 8, 1989; all incorporated herein by reference.

BRIEF SUMMARY OF THE INVENTION Technical Field

This invention relates to a process for making amines having a highyield weight percent of linear triethylenetetramine (L-TETA) andaminoethylethanolamine (AEEA) by condensing an amino compound in thepresence of a condensation catalyst selected from a Group IVB metaloxide, a Group VIB metal-containing substance and a promotedcondensation catalyst.

This invention also relates to an alkyleneamines producers compositionrich in L-TETA and AEEA.

Background of the Invention

There is a substantial body of literature directed to the use of variousacid catalysts to effect intramolecular and intermolecular condensationof amino compounds. U.S. Pat. No. 2,073,671 and U.S. Pat. No. 2,467,205constitute early prior work on the use of acid condensation catalysts tocondense amino compounds. U.S. Pat. No. 2,073,671 discusses, in ageneral fashion, the catalytic intermolecular condensation of alcoholsand amines or ammonia using the same phosphate catalysts later favoredby U.S. Pat. No. 2,467,205 for the intramolecular condensation ofamines. The two patents are not in harmony over the use of othermaterials as catalysts. To illustrate this point, U.S. Pat. No.2,073,671 states:

"Alumina, thoria, blue oxide of tungsten, titania, chromic oxide, blueoxide of molybdenum and zirconia have been mentioned in the literaturefor use as catalysts in carrying out these reactions but theireffectiveness is so low that no practical application has been made oftheir use."

whereas U.S. Pat. No. 2,467,205 in describing the self-condensation ofethylenediamine (EDA) under vapor phase conditions, to initially produceethyleneamines, but after recycle, eventually generates piperazine (PIP)through multistep condensation reactions, followed by deamination,recommends "dehydration catalysts" which are thereafter characterized as

"silica gel, titania gel, alumina, thoria, boron phosphate, aluminumphosphate, and the like."

U.S. Pat. No 2,073,671 describes the condensation catalyst in thefollowing terms:

". . . a heated catalyst or contact mass containing phosphorus andespecially one or more of the oxygen acids of phosphorus, theiranhydrides, their polymers, and their salts; for example,orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid,phosphorous pentoxide, dimetaphosphoric acid, trimetaphosphoric acid,primary ammonium phosphate, secondary ammonium phosphate, normalammonium phosphate, ammonium metaphosphate, secondary ammoniumpyrophosphate, normal ammonium pyrophosphate, aluminum phosphate,aluminum acid phosphate and mixtures of two or more of such materials."

whereas U.S. Pat. No. 2,467,205 describes one of the preferred catalystsas "basic aluminum phosphate".

U.S. Pat. No. 2,454,404 describes the "catalytic deamination of alkylenepolyamines" by reacting DETA vapor over solid catalysts such asactivated alumina, bauxite, certain aluminum silicates such as kaolinand oxides of thorium, titanium and zirconium.

U.S. Pat. Nos. 2,073,671 and 2,467,205 demonstrate a common experiencein using aluminum phosphate as a condensation catalyst to producealiphatic amines, and U.S. Pat. Nos. 2,454,404 and 2,467,205 contemplatethe other solid catalysts for deamination of amines to make heterocyclicnoncyclic amines. In general, the reaction conditions under whichdeamination to effect cyclization occurs are more severe than thoseemployed for condensation to generate noncyclic molecules, all otherfactors being comparable.

U.S. Pat. Nos. 4,540,822, 4,584,406 and 4,588,842 depict the use ofGroup IVB metal oxides as supports for phosphorus catalysts used toeffect the condensation of amino compounds with alkanolamines.

U.S. Pat. No. 4,683,335 describes the use of tungstophosphoric acid,molybdophosphoric acid or mixtures deposited on titania as catalysts forthe condensation of amines and alkanolamines to makepolyalkylenepolyamines.

U.S. Pat. Nos. 4,314,083, 4,316,840, 4,362,886 and 4,394,524 disclosethe use of certain metal sulfates as useful catalysts for thecondensation of alkanolamine and an amino compound. No distinction ismade between the sulfur compounds in respect to catalytic efficacy.Sulfuric acid is as good as any metal sulfate, and all metal sulfatesare treated as equivalents. At column 8 of U.S. Pat. No. 4,314,083, itis noted that boron sulfate "gave extremely high selectivity at a lowlevel" of EDA. However, selectivity in general was shown to increasewith an increase of EDA relative to monoethanolamine (MEA) in the feed.The only specific metal sulfates disclosed in the patents are antimonysulfate, beryllium sulfate, iron sulfate and aluminum sulfate.

In the typical case of the manufacture of alkyleneamines, mixtures withother alkyleneamines (including a variety of polyalkylenepolyamines andcyclic alkylenepolyamines) are formed. The same holds true when theobject of the process is to produce polyalkylenepolyamines whetheracyclic or cyclic, in that a variety of amino compounds are also formed.Each of these cyclic and acyclic alkyleneamines can be isolated from themixture.

The acid catalyzed condensation reaction involving the reaction of analkanolamine with an amino compound in the presence of an acidiccatalyst is believed to proceed through the mechanism of esterifyingfree surface hydroxyl groups on the acid catalyst with the alkanolamineand/or by protonating the alkanolamine in the presence of the acidcatalyst, followed by loss of water and amine condensation of the esteror the hydrated species, as the case may be, to form the alkyleneamine.Illustrative prior art directed primarily to the cyclicpolyalkylenepolyamines (heterocyclic polyamines), but not necessarilylimited to the aforementioned acid condensation reaction, are: U.S. Pat.Nos. 2,937,176, 2,977,363, 2,977,364, 2,985,658, 3,056,788, 3,231,573,3,167,555, 3,242,183, 3,297,701, 3,172,891, 3,369,019, 3,342,820,3,956,329, 4,017,494, 4,092,316, 4,182,864, 4,405,784 and 4,514,567;European Patent Applications 0 069 322, 0 111 928 and 0 158 319; EastGerman Patent No. 206,896; Japanese Patent Publication No. 51-141895;and French Patent No. 1,381,243. The evolution of the art to the use ofthe acid catalyzed condensation reaction to generate acyclicalkyleneamines, particularly acyclic polyalkylenepolyamines, as thepredominant products stemmed from the initial disclosure in U.S. Pat.No. 4,036,881, though earlier patent literature fairly wellcharacterized such an effect without labeling it so, see U.S. Pat. No.2,467,205, supra. The acid catalysts are phosphorus compounds and thereaction is carried out in the liquid phase. The trend in this catalystdirection was early set as demonstrated by U.S. Pat. Nos. 2,073,671 and2,467,205, supra. A modification of this route includes the addition ofammonia to the reaction, see, for example, U.S. Pat. No. 4,394,524 andU.S. Pat. No. 4,463,193 for the purpose of converting alkanolamine suchas MEA in situ to alkylene amine such as EDA by reaction with ammonia,and the EDA is in situ reacted with MEA according to the process of U.S.Pat. No. 4,036,881 to form alkyleneamines.

A summary of the prior art employing acid catalysts for makingalkyleneamines is set forth in Table I below.

                  TABLE I                                                         ______________________________________                                        CITATION  CATALYST TYPE   REACTANTS                                           ______________________________________                                        U.S. Pat. No.                                                                           Silica gel, titania gel,                                                                      Vapor phase conden-                                 2,467,205 alumina, thoria,                                                                              sation of EDA over a                                          aluminum phosphate.                                                                           fixed bed of the cata-                                        Preferred catalyst is                                                                         lyst, multipass process                                       basic aluminum phos-                                                                          shifts from polyethyl-                                        phate.          ene-polyamines with                                                           the first few cycles.                               U.S. Pat. No.                                                                           Phosphorus containing                                                                         Alkanolamine and                                    4,036,881 substances selected from                                                                      alkyleneamine in                                              the group consisting of                                                                       liquid phase reaction.                                        acidic metal phosphates,                                                      phosphoric acid com-                                                          pounds and their anhy-                                                        drides, phosphorus acid                                                       compounds and their                                                           anhydrides, alkyl or aryl                                                     phosphate esters, alkyl                                                       or aryl phosphite esters,                                                     alkyl or aryl substituted                                                     phosphorous and phos-                                                         phoric acids wherein                                                          said alkyl groups have                                                        from 1 to about 8 carbon                                                      atoms and said aryl                                                           groups have from 6 to                                                         about 20 carbon atoms,                                                        alkali metal monosalts                                                        of phosphoric acid, the                                                       thioanalogs of the fore-                                                      going, and mixtures of                                                        the above.                                                          U.S. Pat. No.                                                                           Phosphorus containing                                                                         Alkanepolyols and                                   4,044,053 substances selected from                                                                      alkyleneamine in                                              the group consisting of                                                                       liquid phase reaction.                                        acidic metal phosphates,                                                      phosphoric acid com-                                                          pounds and their anhy-                                                        drides, phosphorus acid                                                       compounds and their                                                           anhydrides, alkyl or aryl                                                     phosphate esters, alkyl                                                       or aryl phosphite esters,                                                     alkyl or aryl substituted                                                     phosphorous acids and                                                         phosphoric acids where-                                                       in said alkyl groups have                                                     from 1 to about 8 carbon                                                      atoms and said aryl                                                           groups have from 6 to                                                         about 20 carbon atoms,                                                        alkali metal monosalts of                                                     phosphoric acid and                                                           mixtures of the above.                                              U.S. Pat. No.                                                                           Salt of a nitrogen or                                                                         Alkanolamine and an                                 4,314,083 sulfur containing sub-                                                                        alkyleneamine in                                              stance or the corres-                                                                         liquid phase reaction.                                        ponding acid.                                                       U.S. Pat. No.                                                                           Metal nitrates and sul-                                                                       Reforming linear                                    4,316,840 fates including zirconium                                                                     polyamines.                                                   sulfate.                                                            U.S. Pat. No.                                                                           Phosphate, preferably                                                                         Reforming linear                                    4,316,841 boron phosphate.                                                                              polyamines.                                         U.S. Pat. No.                                                                           Phosphorus-containing                                                                         Alkanolamine and an                                 4,324,917 cation exchange resin.                                                                        alkyleneamine in                                                              liquid phase reaction.                              U.S. Pat. No.                                                                           Arsenic, antimony or                                                                          Alkanolamine and an                                 4,362,886 bismuth containing com-                                                                       alkyleneamine in                                              pounds. Antimony sul-                                                                         liquid phase reaction.                                        fate specifically dis-                                                        closed.                                                             U.S. Pat. No.                                                                           Lewis acid halide.                                                                            Alkanolamine and an                                 4,399,308                 alkyleneamine in                                                              liquid phase reaction.                              U.S. Pat. No.                                                                           Phosphorus-containing                                                                         Ammonia, alkanol-                                   4,394,524 substance or salt of a                                                                        amine and an alkyl-                                           sulfur-containing sub-                                                                        eneamine in liquid                                            stance, or the corres-                                                                        phase reaction.                                               ponding acid.                                                       U.S. Pat. No.                                                                           Reacts alimina with                                                                           EDA with MEA.                                       4,448,997 phosphoric acid, adds                                                         ammonium hydroxide.                                                 U.S. Pat. No.                                                                           Group IIIB metal acid                                                                         Ammonia, alkanol-                                   4,463,193 phosphate.      amine and an                                                                  alkyleneamine.                                      U.S. Pat. No.                                                                           Supported phosphoric                                                                          Ammonia, alkanol-                                   4,503,253 acid.           amine and an                                                                  alkyleneamine.                                      U.S. Pat. No.                                                                           Select hydrogen phos-                                                                         Alkanolamine and an                                 4,521,600 phates and pyrophos-                                                                          alkyleneamine.                                                phates.                                                             U.S. Pat. No.                                                                           Phosphorus impregnated                                                                        Alkanolamine and an                                 4,524,143 onto zirconium silicate                                                                       alkyleneamine.                                                support.                                                            U.S. Pat. No.                                                                           Phosphorus compound                                                                           Alkanolamine and an                                 4,540,822 deposited on a Group                                                                          alkyleneamine, regen-                                         IVB metal oxide erates the catalyst                                           support.        with O.sub.2 -containing                                                      gas.                                                U.S. Pat. No.                                                                           Silica-alumina alone or                                                                       An ethyleneamine and                                4,547,591 in combination with an                                                                        an alkanolamine;                                              acidic phosphorus                                                                             ethyleneamines; or                                            cocatalyst.     ammonia and an                                                                alkanolamine.                                       U.S. Pat. No.                                                                           An intercalatively cata-                                                                      EDA and MEA.                                        4,550,209 lytically active tetra-                                                       valent zirconium poly-                                                        meric reaction product of                                                     an organo phosphonic                                                          acid or an ester thereof                                                      with a compound of                                                            tetravalent zirconium                                                         reactive therewith.                                                 U.S. Pat. No.                                                                           Phosphorus amide                                                                              Alkyleneamine and                                   4,552,961 compound.       alkanolamine and/or                                                           alkylene glycol.                                    U.S. Pat. No.                                                                           Phosphorus chemically                                                                         MEA and EDA.                                        4,555,582 bonded to a zirconium                                                         silicate support.                                                   U.S. Pat. No.                                                                           Rare earth metal or                                                                           MEA.                                                4,560,798 strontium acid phos-                                                          phate.                                                              U.S. Pat. No.                                                                           Group IIIB metal acid                                                                         Ammonia or p-/s-                                    4,578,517 phosphate.      amine and                                                                     alkanolamine.                                       U.S. Pat. No.                                                                           Thermally activated,                                                                          MEA and EDA.                                        4,578,518 calcined, pelleted titania                                                    containing titanium tri-                                                      phosphte. ". . . the                                                          titania that was used was                                                     . . . anatase."                                                               (Col. 9, lines 18-19).                                              U.S. Pat. No.                                                                           Thermally activated,                                                                          MEA and EDA                                         4,578,519 calcined, pelleted titania                                                                    with optional                                                 with chemically bonded                                                                        recycle of DETA.                                              phosphorus derived from                                                       polyphosphoric acid.                                                U.S. Pat. No.                                                                           Activated carbon, op-                                                                         MEA and EDA.                                        4,584,405 tionally treated to in-                                                       corporate phosphorus.                                                         Activated carbon may                                                          be washed with strong                                                         mineral acid to remove                                                        impurities followed by                                                        water wash. Optional                                                          treatment follows.                                                  U.S. Pat. No.                                                                           Pelleted Group IVB                                                                            MEA and EDA.                                        4,584,406 metal oxide with                                                              chemically bonded phos-                                                       phorus derived from                                                           phosphoryl chloride or                                                        bromide.                                                            U.S. Pat. No.                                                                           Thermally activated                                                                           MEA and EDA.                                        4,588,842 pelleted Group IVB                                                            metal oxide with                                                              chemically bonded                                                             phosphorus.                                                         U.S. Pat. No.                                                                           Group IIA or IIIB                                                                             Alkanolamine and an                                 4,605,770 metal acid phosphate.                                                                         alkyleneamine "in                                                             liquid phase".                                      U.S. Pat. No.                                                                           Thermally activated                                                                           MEA and EDA.                                        4,609,761 pelleted titania with                                                         chemically bonded                                                             phosphorus.                                                         U.S. Pat. No.                                                                           Thermally activated                                                                           MEA and EDA.                                        4,612,397 pelleted titania with                                                         chemically bonded                                                             phosphorus.                                                         U.S. Pat. No.                                                                           Acid catalysts, mentions                                                                      Ammonia, alkanol-                                   4,617,418 "beryllium sulfate".                                                                          amine and an                                                                  alkyleneamine                                                                 "under vapor phase                                                            conditions".                                        Japanese Patent                                                                         Variety of phosphorus                                                                         Ammonia, alkanol-                                   Application                                                                             and metal phosphates                                                                          amine and ethylene-                                 #1983-185,871,                                                                          including Group IVB                                                                           amine, with ammonia/                                Publication                                                                             phosphates.     alkanolamine molar                                  #1985-78,945              ratio greater than 11.                              U.S. Pat. No.                                                                           Tungstophosphoric acid,                                                                       Claims reaction of                                  4,683,335 molybdophosphoric acid                                                                        MEA and EDA, but                                              or mixtures deposited on                                                                      discloses self-con-                                           titania. Examples 2-7                                                                         densation reaction                                            characterize titania sur-                                                                     of EDA and DETA.                                              face areas of 51, 60 and                                                      120 m.sup.2 /gm.                                                    Japanese Patent                                                                         Group IVB metal oxide                                                                         Ammonia and MEA.                                    Application                                                                             with bonded phosphorus.                                             #1985-078,391,                                                                Publication                                                                   #1986-236,752                                                                 Japanese Patent                                                                         Group IVB metal oxide                                                                         Ammonia and MEA.                                    Application                                                                             with bonded phosphorus.                                             #1985-078,392,                                                                Publication                                                                   #1986-236,753                                                                 U.S. Pat. No.                                                                           Titania having phos-                                                                          Diethanolamine and/                                 4,698,427 phorus thermally chem-                                                                        or hydroxyethyldi-                                            ically bonded to the sur-                                                                     ethylenetriamine                                              face thereof in the form                                                                      in EDA.                                                       of phosphate bonds.                                                 U.S. Pat. No.                                                                           Pelleted Group IVB                                                                            MEA and EDA.                                        4,806,517 metal oxide with phos-                                                        phorus thermally chemi-                                                       cally bonded to the                                                           surface thereof.                                                    European  Titania and zirconia                                                                          MEA and EDA.                                        Patent    chemically bonded to                                                Application                                                                             phosphorus.                                                         331,396                                                                       ______________________________________                                    

A summary of additional prior art for making alkyleneamines is set forthin Table II below.

                  TABLE II                                                        ______________________________________                                        CITATION   CATALYST TYPE  REACTANTS                                           ______________________________________                                        Japanese Patent                                                                          Niobium-containing                                                                           Ammonia, alkylene-                                  Application                                                                              substance.     amine and alkylene                                  #1987-312,182,            glycol.                                             Publication                                                                   #1989-153,659                                                                 Japanese Patent                                                                          Niobium-containing                                                                           Ammonia, alkylene-                                  Application                                                                              substance added                                                                              amine and                                           #1987-325,274,                                                                           to water-containing                                                                          alkanolamine. -Publication liquid.                  #1989-168-647                                                                 Japanese Patent                                                                          Niobium oxide  Ammonia, alkylene-                                  Application                                                                              obtained from  amine and                                           #1987-321,348,                                                                           niobium alkoxide.                                                                            alkanolamine.                                       Publication                                                                   #1989-163,159                                                                 Japanese Patent                                                                          Niobium pentoxide.                                                                           Ammonia, alkylene-                                  Application               amine and                                           #1989-314,132,            dialkanolamine.                                     Publication                                                                   #1989-157,936                                                                 Japanese Patent                                                                          Niobium-containing                                                                           Ammonia, alkylene-                                  Application                                                                              substance.     amine and                                           #1987-290,652,            alkanolamine.                                       Publication                                                                   #1989-132,550                                                                 Japanese Patent                                                                          Tantalum-containing                                                                          Ammonia, alkylene-                                  Application                                                                              substance.     amine and                                           #1987-142,284,            alkanolamine.                                       Publication                                                                   #1988-307,846                                                                 European Patent                                                                          Mixed oxide con-                                                                             Ammonia, alkylene-                                  Application                                                                              taining niobium                                                                              amine and                                           315,189    oxide.         alkanolamine.                                       European Patent                                                                          Niobium-containing                                                                           Ammonia, alkylene-                                  Application                                                                              substance supported                                                                          amine and                                           328,101    on a carrier   alkanolamine.                                       Japanese Patent                                                                          Titania and zirconia                                                                         MEA and EDA.                                        Application                                                                              chemically bonded                                                  #1989-048,699,                                                                           with phosphorus in                                                 Publication                                                                              the form of a                                                      #1990-006,854                                                                            hydroxy-containing                                                            phosphate group.                                                   Japanese Patent                                                                          Niobium oxide  Ammonia, alkylene-                                  Application                                                                              and titania,   amine and                                           #1988-262,861,                                                                           alumina, silica                                                                              alkanolamine.                                       Publication                                                                              or zirconia.                                                       #1990-002,876                                                                 Japanese Patent                                                                          Niobium oxide  Ammonia, alkylene-                                  Application                                                                              treated with   amine and                                           #1988-290,106,                                                                           and acid.      alkanolamine.                                       Publication                                                                   #1990-000,735                                                                 Japanese Patent                                                                          Niobium-containing                                                                           Ammonia, alkylene-                                  Application                                                                              substance on   amine and                                           #1988-027,489,                                                                           a carrier.     alkanolamine.                                       Publication                                                                   #1990-000,736                                                                 Japanese Patent                                                                          Three constituent                                                                            Alcohol or alde-                                    Application                                                                              catalyst-copper; one                                                                         hyde and ammonia,                                   #1988-261,366                                                                            or more elements                                                                             a primary amine or                                  Publication                                                                              selected from chro-                                                                          a secondary amine.                                  #1990-000,232                                                                            mium, manganese,                                                              iron and zinc; and a                                                          platinum group                                                                element.                                                           Japanese Patent                                                                          Four constituent                                                                             Alcohol or alde-                                    Application                                                                              catalyst-copper; one                                                                         hyde and ammonia,                                   #1988-261,368,                                                                           or more elements                                                                             a primary amine or                                  Publication                                                                              selected from chro-                                                                          a secondary amine.                                  #1990-000,233                                                                            mium, manganese,                                                              iron, cobalt, nickel                                                          and zinc; a platinum                                                          group element; and                                                            one or more ele-                                                              ments selected from                                                           lithium, sodium, po-                                                          tassium, rubidium,                                                            cesium, magnesium,                                                            calcium, strontium,                                                           and barium.                                                        Japanese Patent                                                                          Four constituent                                                                             Alcohol or alde-                                    Application                                                                              catalyst-copper; one                                                                         hyde and ammonia,                                   #1988-261,369,                                                                           or more elements                                                                             a primary amine or                                  Publication                                                                              selected from chro-                                                                          a secondary amine.                                  #1990-000,234                                                                            mium, manganese,                                                              iron, cobalt, nickel                                                          and zinc; a platinum                                                          group element; and                                                            one or more ele-                                                              ments selected from                                                           aluminum, tungsten                                                            and molybdenum.                                                    ______________________________________                                    

The market demand for L-TETA and AEEA has been progressively increasingin recent years. It would be desirable to satisfy the existing demandfrom a cost standpoint by modifying slightly the commercial processesdirected to the manufacture of polyalkylene polyamines from suitablestarting raw materials to the production of L-TETA and AEEA as majorproducts.

It would be desirable to have continuously produced compositions,generated by the reaction of ethylene glycol (EG) and EDA or othersuitable starting raw materials over a fixed bed of a condensationcatalyst under commercial conditions, that are rich in L-TETA and AEEAand that are not disproporationately high in PIP and other cyclics.

The above features are provided by this invention.

SUMMARY OF THE INVENTION

This invention relates in general to a process of making amines having ahigh yield weight percent of L-TETA and AEEA which comprises condensingan amino compound in the presence of a condensation catalyst selectedfrom a Group IVB metal oxide, a Group VIB metal-containing substance anda promoted condensation catalyst. The amino compound used hereinpreferably comprises an alkyleneamine and an alkylene glycol, inparticular, EDA and EG. The condensation catalysts used herein containsufficient residual bound hydroxyl groups or other groupings whichrenders catalyst formation possible by loss of water or its chemicalequivalent such as ammonium hydroxide.

More particularly, this invention relates to a process of making amineshaving a high yield weight percent of L-TETA and AEEA by the (i)intramolecular condensation of an amino compound to an amine having alower molecular weight or (ii) the intermolecular condensation of anamino compound with one or more of another amino compound or a compoundcontaining an alcoholic hydroxyl group using a particularly definedcondensation catalyst. The process of this invention primarily involvesintermolecular condensation reactions. A preferred process involves themanufacture of L-TETA and AEEA by an intermolecular condensationreaction utilizing EDA and EG as reactants and a Group VIBmetal-containing substance or a Group IVB metal oxide as thecondensation catalyst.

The invention further relates to a continuously generated alkyleneaminesproducers composition comprising, based on 100 percent of the weight ofthe composition and exclusive of any water and/or ammonia and/or feedpresent,

a) greater than about 10.0 weight percent of L-TETA,

b) greater than about 10.0 weight percent of AEEA,

c) less than about 20.0 weight percent of the combination of PIP andAEP,

d) less than about 30.0 weight percent of others,

e) an AEEA to L-TETA weight ratio of less than about 8.0, and

f) a L-TETA +AEEA to PIP weight ratio of greater than about 5.0.

As used herein, the term "amino compound" embraces ammonia and anycompound containing nitrogen to which is bonded an active hydrogen.Also, as used herein, the term "oxide" embraces oxides, hydroxidesand/or mixtures thereof. Further, as used herein, the term "others"embraces polyalkylene polyamines, byproducts and the like.

For purposes of this invention, the chemical elements are identified inaccordance with the Periodic Table of the Elements, CAS version,Handbook of Chemistry and Physics, 67th Ed., 1986-87, inside cover.Also, for purposes of this invention, Group IIIB metal oxides embracesthe lanthanides and actinides.

DETAILED DESCRIPTION

L-TETA and AEEA are very useful commercial products for a variety ofapplications including fuel oil additives, corrosion inhibitors, fabricsofteners, epoxy curing agents and others. There is a need for theability to commercially generate larger production quantities of L-TETAand AEEA and that is the direction of this invention. The process ofthis invention provides for the reaction of EG and EDA or other suitablestarting raw materials to produce in a continuous manner a reactionproduct mixture, termed herein an "alkyleneamines producerscomposition", in which L-TETA and AEEA are principal products of thereaction.

The process of this invention is distinctive insofar as it achieves thegeneration of high concentrations of L-TETA and AEEA in a manner whichcan be suitably employed in a commercial process, particularly acontinuous process, for the manufacture of alkyleneamines. Inparticular, the process of this invention allows the production ofL-TETA and AEEA in relatively high yields without generating largeamounts of cyclic alkyleneamine products.

As indicated above, this invention relates to a process of making amineshaving a high yield weight percent of L-TETA and AEEA which comprisescondensing an amino compound in the presence of a catalyticallyeffective amount of a condensation catalyst selected from a Group IVBmetal oxide, a Group VIB metal-containing substance and a promotedcondensation catalyst. The amino compound preferably comprises analkyleneamine and an alkylene glycol, in particular, EDA and EG.

As also indicated above, this invention relates to a continuouslygenerated alkyleneamines producers composition comprising, based on 100percent of the weight of the composition and exclusive of any waterand/or ammonia and/or feed present,

a) greater than about 10.0 weight percent of L-TETA,

b) greater than about 10.0 weight percent of AEEA,

c) less than about 20.0 weight percent of the combination of PIP andAEP,

d) less than about 30.0 weight percent of others,

e) an AEEA to L-TETA weight ratio of less than about 8.0, and

f) a L-TETA +AEEA to PIP weight ratio of greater than about 5.0.

The alkyleneamines producers composition of this invention can besubjected to conventional separations techniques for recovering theindividual components of the composition. Such techniques are well knownin the art and include, for example, distillation.

This invention contemplates the catalyzed condensation by (i)intramolecular condensation of an amino compound to an amine having alower molecular weight, and (ii) intermolecular condensation of an aminocompound with one or more of another amino compound or a compoundcontaining an alcohol hydroxyl group to an amine having a lower, same orhigher molecular weight than the reactants, in the presence of aparticularly defined condensation catalyst. The process of thisinvention primarily involves intermolecular condensation reactions.

A wide variety of condensation catalysts can be used in this invention.Illustrative of suitable condensation catalysts for use in thisinvention include, for example, Group IVB metal oxides, Group VIBmetal-containing substances and promoted condensation catalysts.

The Group IVB metal oxide condensation catalysts are preferred catalystsfor use in this invention. Suitable Group IVB metal oxide condensationcatalysts are disclosed in U.S. patent application Ser. No. 07/390,829,filed Aug. 8, 1989 and incorporated herein by reference. Illustrative ofGroup IVB metal oxide condensation catalysts include, for example,titanium oxide and zirconium oxide, preferably titanium dioxide andzirconium dioxide including mixtures thereof.

The Group VIB metal-containing condensation catalysts are also preferredcatalysts for use in this invention. Suitable Group VIB metal-containingcondensation catalysts are disclosed in the above-cited related U.S.patent application Ser. No. 07/390,708, filed Aug. 8, 1989 andincorporated herein by reference. Illustrative of Group VIBmetal-containing condensation catalysts include, for example, one ormore oxides of tungsten, chromium, molybdenum or mixtures thereof.

A variety of promoted condensation catalysts are also desirable for usein this invention. Suitable promoted condensation catalysts aredisclosed in U.S. patent application Ser. No 07/390,714, filed Aug. 8,1989 and incorporated herein by reference. The condensation catalystsare promoted by a condensation catalyst promoter as describedhereinafter. Illustrative of such condensation catalysts include, forexample, one or more Group IVB metal oxides and Group VIBmetal-containing substances.

The condensation catalyst promoter for use in this invention should becapable of promoting the condensation catalyst. The promoting effect canrelate to catalytic activity, product selectivity and/or catalyststability (mechanical or dimensional strength of the catalyst).Illustrative of condensation catalyst promoters for use in thisinvention can include, for example, one or more metal oxides, one ormore metallic phosphates which may or may not have a cyclic structure,one or more metallic polyphosphates having a condensed structure, one ormore Group VIB metal-containing substances and one or more conventionalmaterials such as mineral acids or compounds derived from mineral acids.Mixtures of condensation catalyst promoters may also be employed in thisinvention. For purposes of this invention, the condensation catalystpromoter should be different from the condensation catalyst; however,the condensaton catalyst promoter and the performance moderatordescribed hereinafter can be the same or different.

This invention also embraces the use of vicinal di(hetero)alkyleneorganometalates in the selective preparation of L-TETA and AEEA.Suitable vicinal di(hetero)alkylene organometalates are disclosed inU.S. patent application Ser. No. 07/390,828, filed Aug. 8, 1989 andincorporated herein by reference (now U.S. Pat. No. 5,101,074).

The level of activity of the condensation catalysts of the invention isthat level which of itself makes the catalysts at least as active in thecondensation of amines as, for example, is phosphoric acid on anequivalent basis. Preferably, the condensation catalysts on a supportshould have a surface area greater than about 20 m² /gm to as high asabout 260 m² /gm or greater depending upon which metal oxide describedbelow that is employed. In the case of titanium oxides, the surface areashould be greater than about 140 m² /gm to as high as about 260 m² /gm,more preferably, greater than about 160 m² /gm to as high as about 260m² /gm, determined according to the single point N₂ method. In the caseof zirconia oxides, the surface area should be greater than about 70 m²/gm to as high as about 150 m² /gm, more preferably, greater than about90 m² /gm to as high as about 135 m² /gm, determined according to thesingle point N₂ method It is appreciated that the performance moderatorsdescribed below which can be used in association with the condensationcatalyst and the condensation catalyst promoters described above canaffect the surface area of the condensation catalyst. While surfaceareas described above may be preferred, for purposes of this invention,the surface area of the condensation catalyst should be sufficient tocontribute to product selectivity, catalytic activity and/or mechanicalor dimensional strength of the catalyst.

Though the condensation catalyst of the invention provides sufficientactivity to effect the condensation reaction, certain combinations ofreactants and/or product formation can be benefited by treating thecatalyst with a catalyst moderator, hereinafter termed a "performancemoderator". Performance moderators are widely used to promote theperformance of catalysts in areas of selectivity to certain products andthe repression of a catalyst's proclivity to generate a broad range ofreaction products. A range of suitable materials may impact thecondensation catalysts of this invention in the variety of reactionproducts. The performance moderator may be any material which impactsthe condensation catalyst's selection of reaction products or whichchanges the proportion of any one or more of the reaction products whichthe condensation catalyst generates at comparable processing conditions.In addition to contributing to product selectivity, the performancemoderator may be any material which contributes to catalytic activityand/or catalyst stability (mechanical or dimensional strength).

Illustrative performance moderators for use in this invention caninclude, for example, one or more metal oxides, one or more metallicphosphates which may or may not have a cyclic structure, one or moremetallic polyphosphates having a condensed structure, one or more GroupVIB metal-containing substances and one or more conventional materialssuch as mineral acids or compounds derived from mineral acids. Mixturesof performance moderators may also be employed in this invention. Forpurposes of this invention, the performance moderator should bedifferent from the condensation catalyst; however, the performancemoderator and the condensation catalyst promoter can be the same ordifferent.

Illustrative of metal oxides which may be utilized as performancemoderators in association with the condensation catalyst include, forexample, one or more of the following: Group IA metal oxides, Group IIAmetal oxides, Group IIIB metal oxides (including lanthanides andactinides), Group VB metal oxides, Group VIB metal oxides, Group VIIBmetal oxides, Group VIII metal oxides, Group IB metal oxides, Group IIBmetal oxides, Group IIIA metal oxides, Group IVA metal oxides, Group VAmetal oxides, Group VIA metal oxides and Group IVB metal oxides ormixtures thereof. Certain of these metal oxides may also be used ascondensation catalysts in accordance with this invention such as GroupIVA and IVB metal oxides. Preferred metal oxides are amphoteric orslightly acidic or slightly basic. Preferred metal oxides which may beutilized in association with the condensation catalyst include, forexample, one or more oxides of beryllium, scandium, yttrium, terbium,dysprosium, holmium, erbium, thulium, ytterbium, lutetium, titanium,zirconium, hafnium, vanadium, niobium, tantalum, tungsten, iron, cobalt,zinc, silver, aluminum, gallium, indium, silicon, germanium, tin, lead,arsenic, antimony and bismuth.

Group IVB metal oxides such as titanium dioxide and zirconium dioxideand Group IVA metal oxides such as silica and germania are preferred foruse in this invention. For mixed metal oxides in which at least one ofthe metals is titanium, suitable metals in association with titanium mayinclude, for example, one or more of the following: Group IIIB metalssuch as scandium, yttrium and lanthanum including the lanthanides, GroupVB metals such as niobium and tantalum, Group VIB metals such aschromium, molybdenum and tungsten, Group VIII metals such as iron,cobalt and nickel, Group IIB metals such as zinc and cadmium, Group IIIAmetals such as boron, aluminum, gallium and indium, Group IVA metalssuch as silicon, germanium, tin and lead, Group VA metals such asarsenic, antimony and bismuth, and Group IVB metals such as zirconiumand hafnium. For mixed metal oxides in which at least one of the metalsis zirconium, suitable metals in association with zirconium may include,for example, one or more of the following: Group IVA metals such assilicon, germanium, tin and lead, Group VB metals such as niobium andtantalum, and Group VIB metals such as chromium, molybdenum andtungsten. Certain of these metal oxides may also be effective ascondensation catalysts for use in this invention.

Illustrative of mixed metal oxides which may be used as performancemoderators in association with the condensation catalyst include, forexample, TiO₂ --SiO₂, TiO₂ --Al₂ O₃, TiO₂ --CdO, TiO₂ --Bi₂ O₃, TiO₂--Sb₂ O₅, TiO₂ --SnO₂, TiO₂ --ZrO₂, TiO₂ --BeO, TiO₂ --MgO, TiO₂ --CaO,TiO₂ --SrO, TiO₂ --ZnO, TiO₂ --Ga₂ O₃, TiO₂ --Y₂ O₃, TiO₂ --La₂ O₃, TiO₂--MoO₃, TiO₂ --Mn₂ O₃, TiO₂ --Fe₂ O₃, TiO₂ --Co₃ O₄, TiO₂ --WO₃, TiO₂--V₂ O₅, TiO₂ --Cr₂ O₃, TiO₂ --ThO₂, TiO₂ --Na₂ O, TiO₂ --BaO, TiO₂--CaO, TiO₂ --HfO₂, TiO₂ --Li₂ O, TiO₂ --Nb.sub. 2 O₅, TiO₂ --Ta₂ O₅,TiO₂ --Gd₂ O₃, TiO₂ --Lu₂ O₃, TiO₂ --Yb₂ O₃, TiO₂ --CeO₂, TiO₂ --Sc₂ O₃,TiO₂ --PbO, TiO₂ --NiO, TiO₂ --CuO, TiO₂ --CoO, TiO₂ --B₂ O₃, ZrO₂--SiO₂, ZrO₂ --Al₂ O₃, ZrO₂ --SnO, ZrO₂ --PbO, ZrO₂ --Nb₂ O₅, ZrO₂ --Ta₂O₅, ZrO₂ --Cr₂ O₃, ZrO₂ --MoO₃, ZrO₂ --WO₃, ZrO₂ --TiO₂, ZrO₂ --HfO₂,TiO₂ --SiO₂ --Al₂ O₃, TiO₂ --SiO₂ --ZnO, TiO₂ --SiO₂ --ZrO₂, TiO₂ --SiO₂--CuO, TiO₂ --SiO₂ --MgO, TiO₂ --SiO₂ --Fe₂ O₃, TiO₂ --SiO.sub. 2 --B₂O₃, TiO₂ --SiO₂ --WO₃, TiO₂ --SiO₂ --Na₂ O, TiO₂ --SiO₂ --MgO, TiO₂--SiO₂ --La₂ O₃, TiO₂ --SiO₂ --Nb₂ O₅, TiO₂ --SiO₂ --Mn₂ O₃, TiO₂ --SiO₂--Co₃ O₄, TiO₂ --SiO₂ --NiO, TiO₂ --SiO₂ --PbO, TiO₂ --SiO₂ --Bi₂ O₃,TiO₂ --Al₂ O₃ -ZnO, TiO₂ --Al₂ O₃ --ZrO₂, TiO₂ --Al₂ O₃ --Fe₂ O₃, TiO₂--Al₂ O₃ --WO₃, TiO₂ --Al₂ O₃ --La₂ O₃, TiO₂ --Al₂ O₃ --Co₃ O₄, ZrO₂--SiO₂ --Al₂ O₃, ZrO₂ --SiO₂ --SnO, ZrO₂ --SiO₂ --Nb₂ O₅, ZrO₂ --SiO₂---WO₃, ZrO₂ --SiO₂ --TiO₂, ZrO₂ --SiO₂ --MoO₃, ZrO₂ --SiO₂ --HfO₂, ZrO₂--SiO₂ --Ta₂ O₅, ZrO₂ --Al₂ O₃ --SiO₂, ZrO₂ --Al₂ O₃ --PbO, ZrO₂ --Al₂O₃ --Nb₂ O₅, ZrO₂ --Al₂ O₃ --WO₃, ZrO₂ --Al₂ O₃ --TiO₂, ZrO₂ --Al₂ O₃--MoO₃, ZrO₂ --HfO₂ --Al₂ O₃, ZrO₂ --HfO₂ --TiO₂, and the like. Othersuitable mixed metal oxides embraced within the scope of this inventionare disclosed by Tanabe et al., Bulletin of the Chemical Society ofJapan, Vol. 47(5), pp. 1064-1066 (1974).

The metal oxides described herein which can be used as performancemoderators in association with the condensation catalyst may contributeto product selectivity and/or catalytic activity of the reaction and/orstability of the catalyst. The catalyst structure can comprise fromabout 0 to about 90 percent or greater by weight of the metal oxide,preferably from about 0 to about 75 percent by weight of the metaloxide, and more preferably from about 0 to about 50 percent by weight ofthe metal oxide, the remainder being the weight of the condensationcatalyst. For mixed metal oxides containing titania, higherconcentrations of titania can provide very desirable L-TETA and AEEAselectivities. As discussed hereinafter, the condensation catalyst ofthis invention may also contain support(s), binding agent(s) or otheradditives to stabilize or otherwise help in the manufacture of thecatalyst.

The metallic phosphate and polyphosphate performance moderators may ormay not have a cyclic structure and may or may not have a condensedstructure. Suitable metallic phosphates having a cyclic structure or anacyclic structure are disclosed in U.S. patent application Ser. No.07/390,706, filed Aug. 8, 1989 and incorporated herein by reference.Suitable metallic polyphosphates having a condensed structure aredisclosed in U.S. patent application Ser. No. 07/390,709, filed Aug. 8,1989 and incorporated herein by reference (now U.S. Pat. No. 4,983,736)Illustrative of metallic phosphate and polyphosphate performancemoderators include, for example, metallic orthophosphates (PO₄ ⁻³),metallic pyrophosphates (P₂ O₇ ⁻⁴), metallic polyphosphates (includingtripolyphosphates (P₃ O₁₀ ⁻⁵), tetrapolyphosphates (P₄ O₁₃ ⁻⁶),pentapolyphosphates (P₅ O₁₆ ⁻⁷) and higher polyphosphates), metallicmetaphosphates (including trimetaphosphates (P₃ O₉ ⁻³),tetrametaphosphates (P₄ O₁₂ ⁻⁴) and other lower and highermetaphosphates) and metallic ultraphosphates (condensed phosphatescontaining more P₂ O₅ than corresponds to the metaphosphate structure).Corresponding metallic metaphosphimates, metallic phosphoramidates andmetallic amido- and imidophosphates of the above may also be used asperformance moderators in accordance with this invention. Suitablemetals which can be incorporated into the metallic phosphate andpolyphosphate performance moderators include, for example, Group IAmetals, Group IIA metals, Group IIIB metals, Group IVB metals, Group VBmetals, Group VIB metals, Group VIIB metals, Group VIII metals, Group IBmetals, Group IIB metals, Group IIIA metals, Group IVA metals, Group VAmetals, Group VIA metals and mixtures thereof.

Illustrative of metallic orthophosphates which may be utilized in thisinvention include, for example, NaH₂ PO₄, KH₂ PO₄, RbH₂ PO₄, LiH₂ PO₄,CsH₂ PO₄, MgHPO₄, CaHPO₄, YPO₄, CePO₄, LaPO₄, ThPO₄, MnPO₄, FePO₄, BPO₄,AlPO₄, BiPO₄, Mg(H₂ PO₄)₂, Ba(H₂ PO₄)₂, Mg(NH₄)₂ PO₄, Ca(H₂ PO₄)₂, La(H₂PO₄)₃ and the like. Illustrative of metallic pyrophosphates which may beutilized in this invention include, for example, Na₂ H₂ P₂ O₇, K₂ H₂ P₂O₇, Ca₂ P₂ O₇, Mg₂ P₂ O₇, KMnP₂ O₇, AgMnP₂ O₇, BaMnP₂ O₇, NaMnP₂ O₇,KCrP₂ O₇, NaCrP₂ O₇, Na₄ P₂ O₇, K₄ P₂ O₇ , Na₃ HP₂ O₇, NaH₃ P₂ O₇, SiP₂O₇, ZrP₂ O₇, Na₆ Fe₂ (P₂ O₇)₃, Na₈ Fe₄ (P₂ O₇)₅, Na₆ Cu(P₂ O₇)₂, Na₃₂Cu₁₄ (P₂ O₇)₁₅, Na₄ Cu₁₈ (P₂ O₇)₅, Na(NH₄)₂ P₂ O₇, Ca(NH₄)₂ P₂ O₇, MgH₂P₂ O₇, Mg(NH₄)₂ P₂ O₇) and the like. Illustrative of metallicpolyphosphates which may be utilized in this invention include, forexample, NaSr₂ P₃ O₁₀, NaCa₂ P₃ O₁₀, NaNi₂ P₃ O₁₀, Na₅ P₃ O₁₀, K₅ P₃O₁₀, Na₃ MgP₃ O₁₀, Na₃ CuP₃ O₁₀, Cu₅ (P₃ O₁₀)₂, Na₃ ZnP₃ O₁₀, Na₃ CdP₃O₁₀ , Na₆ Pb(P₃ O₁₀)₂, Na₃ CoP₃ O₁₀, K₃ CoP₃ O₁₀, Na₃ NiP₃ O₁₀, K₂(NH₄)₃ P₃ O₁₀, Ca(NH₄)₂ P₃ O₁₀, La(NH₄)₃ P₃ O₁₀, NaMgH₂ P₃ O₁₀ and thelike. Illustrative of metallic metaphosphates which may be utilized inthis invention include, for example, Na₃ P₃ O₉, K₃ P₃ O₉, Ag₃ P₃ O₉, Na₄P₄ O₁₂, K₄ P₄ O₁₂, Na₂ HP₃ O₉, Na₄ Mg(P₃ O₉)₂, NaSrP₃ O₉, NaCaP₃ O₉,NaBaP₃ O₉, KBaP₃ O₉, Ca₃ (P₃ O₉)₂, Ba(P₃ O₉)₂, Na₂ Ni₂ (P₃ O₉)₂, Na₄Ni(P₃ O₉)₂, Na₄ Co(P₃ O₉)₂, Na₄ Cd(P₃ O₉)₂ and the like. Illustrative ofmetallic ultraphosphates which may be utilized in this inventioninclude, for example, CaP₄ O₁₁, Ca₂ P₆ O₁₇, Na₈ P₁₀ O₂₉, Na₆ P₈ O₂₃, Na₂CaP₆ O₁₇, Na₂ P₄ O₁₁, NaBaP₇ O₁₈, Na₂ P₈ O₂₁, K₄ P₆ O₁₇ and the like.The preferred metallic phosphate and polyphosphate performancemoderators for use in this invention include Group IA metal dihydrogenorthophosphates, Group IA metal metaphosphates and Group IA metaldihydrogen pyrophosphates, more preferably NaH₂ PO₄, Na₃ P₃ O₉, Na₄ P₄O₁₂ and Na₂ H₂ P₂ O₇. Other suitable metallic phosphate andpolyphosphate performance moderators which are embraced within the scopeof this invention are disclosed by Van Wazer, J. R., Phosphorus and ItsCompounds, Vol. 1, Interscience Publishers, Inc., New York (1958).

The metallic phosphate and polyphosphate performance moderators can beprepared by conventional methods known in the art. Sodium is believed tobe one of a small group of cations effective for stabilizingsix-membered cyclic metaphosphates at their temperatures of fusion(about 625° C.) without decomposition to linear and/or other condensedphosphates including mixtures. The formation of cyclic and acyclicmetallic phosphate and polyphosphate structures appears to depend on thecation ionic size, the coordination number of the cation and the ionicor covalent nature of the metal-oxygen bond.

While not wishing to be bound to any particular theory, it is believedthat those metallic phosphate and polyphosphate performance moderatorsand promoters encompassed within the scope of this invention having acyclic structure and possessing ionic character and/or ion exchangecapacity contribute to desired activity and product selectivity whenused in appropriate amounts as described hereinbelow. While the reactionmixture may initially include one or more metallic phosphates and/ormetallic polyphosphates other than metallic phosphates andpolyphosphates having a cyclic structure and possessing ionic characterand/or ion exchange capacity, it is believed to be desirable that suchmetallic phosphates and polyphosphates having a cyclic structure andpossessing ionic character and/or ion exchange capacity be formed insitu in order to contribute to desired activity and product selectivity.In such instances, the preparation conditions or reaction conditionsshould allow for the formation of metallic phosphates and polyphosphateshaving a cyclic structure and possessing ionic character and/or ionexchange capacity. Mixtures of metallic phosphates and polyphosphateshaving a cyclic structure and possessing ionic character and/or ionexchange capacity with metallic phosphates and polyphosphates havingother than a cyclic structure and other than ionic character and/or ionexchange capacity are believed to contribute to desired activity andproduct selectivity.

Illustrative of Group VIB metal-containing substances which can beutilized as performance moderators in association with the condensationcatalyst are described hereinabove. Such Group VIB metal-containingsubstances can contribute to product selectivity, catalytic activityand/or catalyst stability (mechanical or dimensional strength of thecatalyst). Certain of these Group VIB metal-containing substances mayalso be effective as condensation catalysts for use in this invention.

Illustrative of conventional materials which can be utilized asperformance moderators in association with the condensation catalystinclude a mineral acid or a compound derived from a mineral acid.Suitable for use as performance moderators are one or more phosphoricacid or a salt of phosphoric acid, hydrogen fluoride, hydrofluoric acidor a fluoride salt, sulfuric acid or a salt of sulfuric acid, and thelike. The performance moderator may also be organic esters of phosphoricacid or a salt of phosphoric acid, hydrogen fluoride organic complexes,hydrofluoric acid organic complexes or a fluoride salt organiccomplexes, organic esters of sulfuric acid or a salt of sulfuric acid,and the like. Suitable salts of phosphoric acid include sodiumdihydrogen phosphate, disodium hydrogen phosphate and the like.

A variety of conventional phosphorus-containing substances may besuitable for use as performance moderators in this invention. Theconventional substances should be capable of functioning as aperformance moderator. Illustrative of conventionalphosphorus-containing substances may include, for example, thosedisclosed in U.S. Pat. No. 4,036,881, U.S. Pat. No. 4,806,517, U.S. Pat.No. 4,617,418, U.S. Pat. No. 4,720,588, U.S. Pat. No. 4,394,524, U.S.Pat. No. 4,540,822, U.S. Pat. No. 4,588,842, U.S. Pat. No. 4,605,770,U.S. Pat. No. 4,683,335, U.S. Pat. No. 4,316,841, U.S. Pat. No.4,463,193, U.S. Pat. No. 4,503,253, U.S. Pat. No. 4,560,798 and U.S.Pat. No. 4,578,517.

Suitable conventional phosphorus-containing substances which can beemployed as performance moderators in this invention include acidicmetal phosphates, phosphoric acid compounds and their anhydrides,phosphorous acid compounds and their anhydrides, alkyl or aryl phosphateesters, alkyl or aryl phosphite esters, alkyl or aryl substitutedphosphorous acids and phosphoric acids, alkali metal monosalts ofphosphoric acid, the thioanalogs of the foregoing, and mixtures of anyof the above.

For purposes of this invention, the phosphorus-containing substancesused as promoters and performance moderators herein should only beemployed in amounts sufficient so as to not adversely affect AEEAproduct selectivity. While not wishing to be bound to any particulartheory, it is believed that phosphorus-containing substances arecatalytically selective for the reaction of AEEA and an alkyleneaminesuch as EDA to higher polyalkylene polyamines. Therefore, the amount ofa phosphorus-containing substance used as a promoter or performancemoderator herein is considered important to achieving amines productshaving a high yield weight percent of L-TETA and AEEA.

The amount of the performance moderator of the mineral acid type usedwith the condensation catalyst of the invention is not narrowlycritical. Generally, the amount does not exceed 25 weight percent of theweight of the catalyst. As a rule, it is desirable to use at least 0.01weight percent of the weight of the catalyst. Preferably, the amount ofperformance moderator will range from about 0.2 to about 10 weightpercent of the weight of the catalyst. Most preferably, the amount ofperformance moderator will range from about 0.5 to about 5 weightpercent of the weight of the catalyst.

The amount of performance moderator other than the mineral acid typeused with the condensation catalyst is not narrowly critical. Generally,the amount does not exceed 90 weight percent of the weight of thecatalyst. The amount of performance moderator can range from about 0 toabout 90 or greater weight percent of the weight of the catalyst,preferably from about 0 to about 75 weight percent of the weight of thecatalyst, and more preferably from about 0 to about 50 weight percent ofthe weight of the catalyst. Most preferably, the amount of performancemoderator will range from about 0.5 to about 25 weight percent of theweight of the catalyst.

The performance moderator can be provided to the condensation catalystby conventional procedures known in the art. For example, theperformance moderator can be provided to the catalyst by impregnatingparticles or monolithic structures comprising the catalyst with liquidcomprising the performance moderator. This is a well known procedure inthe art for incorporating additives to a solid support material. Thecondensation catalyst of the invention may be utilized as solid powdersor as fused, bonded or compressed solid pellets, or larger structures inassociation with the one or more metal oxides, or as coated, fused,bonded or compressed solid pellets, or larger structures, compositedwith one or more support materials, in association with one or moremetal oxides. These solid structures may be treated with the performancemoderator by mixing a liquid body of the performance moderator with thesolid structure. For example, the condensation catalyst solids may beslurried in the performance moderator, drained, washed and suctioned toremove excess performance moderator and then dried with heat to removeany volatiles accompanying the performance moderator. The dryingtemperature chosen will depend on the nature of the volatiles to beremoved. Usually, the time/temperature for effecting drying will bebelow the conditions for effecting dehydration to remove bound waterfrom the metal oxide in association with the condensation catalyst.Normally the drying temperature will be greater than about 120° C. andbelow about 600° C. depending on the thermal stability of the catalystor the fusion temperature of the particular phosphate specie used ifany. The drying time will generally go down as the drying temperaturerises and vice versus, and may extend from 5 seconds to about 24 hours.

Alternatively, the performance moderator can be provided to thecondensation catalyst at the time of preparing the catalyst inassociation with one or more metal oxides. For example, one or moremetal oxides may be condensed from their respective hydrolyzablemonomers to the desired oxides to form oxide powders which canthereafter be blended and compressed with the catalyst to form pelletsand larger structures of the metal oxide-containing condensationcatalyst of this invention. The one or more metal oxides which can beused in association with the condensation catalyst in accordance withthis invention can be provided from metal salts which can be heated toform the metal oxide. It is appreciated that the performance moderatorcan be incorporated into the molecular bonding configuration of themetal oxide-containing condensation catalyst by conventional proceduresknown in the art.

The condensation catalysts in association with one or more metal oxidesprior to the optional treatment of the performance moderator may beprepared in a wide variety of ways. For example, one or more metaloxides may be provided as a partial condensate on a support, such as asilica or alpha, beta or gamma alumina, silicon carbide, and the like,and then condensed by heating to effect polymerization to the desiredoxide form. The metal oxide(s) may be condensed from hydrolyzablemonomers to the desired oxide, indeed, to form an oxide powder which canthereafter be compressed in the presence of a condensation catalyst toform pellets and larger structures of the metal oxide-containingcondensation catalyst of the invention. A blend of the powder andcondensation catalyst can be made into a shapeable paste which can beextruded and cut into pellets according to conventional procedures. Theextrudate may thereafter be fired to cure the condensation catalyst andfix the structure. The cut extrudate may be blended with a supportmaterial such as those characterized above, and the blend fired to fusethe metal oxide-containing catalyst to the support.

In a preferred embodiment of this invention, a high surface area silica,germania, titania or zirconia can be slurried with an aqueous solutionof ammonium metatungstate or silicotungstic acid, extruded, and calcinedat a temperature of about 400° C.

A preferred catalyst structure comprises a Group VIB and/or IVB metaloxide having a surface area of at least about 140 m² /gm which may ormay not be bonded to a support material. The term "support," as usedherein and in the claims, means a solid structure which does notadversely affect the catalytic properties of the catalyst and is atleast as stable as the catalyst to the reaction medium. The support canfunction as an amine condensation catalyst independent of thecondensation catalyst used herein, although it may have lower catalyticactivity to the reaction. The support may act in concert with thecatalyst to moderate the reaction. Some supports may contribute to theselectivity of the reaction. The catalyst structure can comprise fromabout 2 to about 60 percent by weight or greater of the support, morepreferably from about 10 to about 50 percent by weight of the support,the remainder being the weight of the metal oxide(s) and condensationcatalyst. Included in the weight of the support is the weight of anybinding agent such as phosphates, sulfates, silicates, fluorides, andthe like, and any other additive provided to stabilize or otherwise helpin the manufacture of the catalyst. The support may be particles aslarge or larger than the catalyst component and "glued" to thecondensation catalyst and/or metal oxide by virtue of a binding medium.

The support may constitute a separate phase in the process of extrudingthe catalytic structure. In this embodiment, the support formingmaterial, preferably as a paste is blended with a paste of thecondensation catalyst and one or more metal oxides or a partialcondensate thereof. The paste may comprise the oxide forms of thesupport and the condensation catalyst, each blended with water, and/orbinding agents. The extrudate of the blend is passed through amultiorificed die and chopped into pellets of the desired sizes. Theparticles may be doughnut shaped, spherical, and the like. Then theparticles are calcined to dry them and complete any condensationreaction in the support and/or the metal oxide-containing condensationcatalyst.

The use of supports for the condensation catalyst provides a number ofsignificant advantages. It has been determined that some of thecondensation catalysts are not as stable in the amines reaction mediawhen utilized over an extended period of time. When the reaction iseffected as a batch reaction, this matter is not a problem. However,when the reaction is effected with the condensation catalyst as part ofa fixed bed in a tubular reactor, the preferred procedure for carryingout the invention, it is desirable to have the catalyst be more stable.When the condensation catalyst is combined with the support, it hasgreater stability for the reaction medium, and therefore, it is betterable to be used in a fixed bed of a continuous reactor. The supportedcatalysts suffer only minimally from the leaching problems that thecatalyst per se may have or the problems that are associated withcertain conventional catalysts, such as acidic phosphorus compounds onsilica.

The reactants used in the condensation process of the invention may beammonia or organic compound containing --NH-- and any compoundpossessing an alcoholic hydroxyl group, subject to the following: theintramolecular condensation of an amino compound produces an aminehaving a lower molecular weight, and the intermolecular condensation ofan amino compound with one or more of another amino compound or acompound containing an alcoholic hydroxyl group produces an amine havinga lower, same or higher molecular weight than the reactants.

Illustrative of suitable reactants in effecting the overall process ofthe invention, include by way of example:

Ammonia

DEA--diethanolamine

EG--ethylene glycol

MEA--monoethanolamine

DiHEED--dihydroxyethylethylenediamine

EDA--ethylenediamine

MeEDA--methylethylenediamine

EtEDA--ethylethylenediamine

AEEA--N-(2-aminoethyl)ethanolamine

HEP--N-(2-hydroxyethyl)piperazine

DETA--diethylenetriamine

HEDETA--hydroxyethyldiethylenetriamine

HETETA--hydroxyethyltriethylenetetramine

HETEPA--hydroxyethyltetraethylenepentamine

AEP--N-(2-aminoethyl)piperazine

PEHA--pentaethylenehexamine

PEHA Isomers

HEHA--hexaethylenepentamine

HEHA Isomers

HEOA--heptaethyleneoctamine

HEOA--Isomers

HPA--higher polyalkylene polyamines

HPA Isomers

TETA Isomers (TETA's):

TAEA--trisaminoethylamine

TETA--triethylenetetramine

DPE--dipiperazinoethane

DAEP--diaminoethylpiperazine

PEEDA--piperazinoethylethylenediamine

TEPA Isomers (TEPA's):

AETAEA--aminoethyltrisaminoethylamine

TEPA--tetraethylenepentamine

AEDPE--aminoethyldipiperazinoethane

AEDAEP--aminoethyldiaminoethylpiperazine

AEPEEDA--aminoethylpiperazinoethylethylenediamine

iAEPEEDA--isoaminoethylpiperazinoethylethylenediamine

BPEA--bispiperazinoethylamine

The foregoing also can represent the products of the reaction. Forexample, ammonia and MEA are frequently employed to produce EDA alongwith a variety of other amines, most of which are set forth above.Further, alkylene oxides such as ethylene oxide can be employed withammonia and a variety of other amines to produce polyalkylene polyaminesin accordance with this invention.

Glycol compounds can also be employed in the preparation of amines inaccordance with this invention. Glycol compounds embrace diols andpolyols. Illustrative of glycol compounds include alkylene glycols suchas ethylene glycol, propylene glycol, 1,3-propane diol or mixturesthereof. For purposes of this invention, suitable glycol compoundsinclude ethylene glycol.

The feed space velocity, feed mole ratio and reaction temperature andpressure are not narrowly critical and can vary over a wide range. Theselection of these operating variables is dependent on desiredconversions and product selectivity.

In particular, when EG and EDA are employed as reactants in the processof this invention, an increase in EG space velocity or EDA/EG feed moleratio will decrease conversion, while an increase in temperature willincrease conversion. Typically, it is desired to operate at a highenough pressure to maintain the reactants primarily in the liquid phase.At a particular EG space velocity, EDA/EG feed mole ratio andtemperature, the conversion will generally decrease if the pressure islowered until the flow changes from liquid to vapor.

Lower reaction temperatures generally provide higher selectivity todesired products. As the EDA/EG feed mole ratio increases, theselectivity to desired products increases. The EDA/EG feed mole ratiomay be used to adjust the relative amounts of L-TETA and AEEA. As theEDA/EG feed mole ratio is increased, the L-TETA to AEEA weight ratioincreases.

The process may be effected in the liquid or vapor or supercriticalliquid states or mixtures thereof though the actual reaction is believedto occur on the catalyst's solid surface in the absorbed state. In thiscontext, the vapor phase reaction is intended to refer to the generalvapor state of the reactants. Though the reaction conditions may rangefrom subatmospheric to superatmospheric conditions, it is desirable torun the reaction from about 50 psig to about 3,000 psig, preferably fromabout 200 psig to about 2,000 psig.

The temperature of the reaction may be as low as about 125° C. to about400° C. Preferably, the reaction temperature ranges from about 150° C.to about 350° C., and most preferably from about 225° C. to about 325°C.

The reaction may be effected by the incremental addition of one of thereactants to the other or by the joint addition of the reactants to thecatalyst. The preferred process effects the reaction in a continuousmanner over a fixed bed of the condensation catalyst in a tubularreactor. However, the reaction may be carried out by slurrying thecatalyst in the reactants or in a batch mode in an autoclave. An inertsuch as nitrogen, methane, hydrogen and the like can be used in thereaction process.

The process of the invention provides the ability to selectivelygenerate the manufacture of desirable L-TETA and AEEA without generatinglarge amounts of cyclic alkyleneamine products such as PIP, AEP and HEP.The alkyleneamines producers composition of this invention has a L-TETA+AEEA to PIP weight ratio of greater than about 5.0 and an AEEA toL-TETA weight ratio of less than about 8.0.

This invention is further illustrated by certain of the followingexamples:

EXAMPLES

In the examples set forth in the tables below, the catalyst of choicewas placed in a tubular reactor having an outside diameter of 1 inch andan overall length of 30 inches. The catalyst portion of the reactorcomprised a length of 24 inches, capable of accommodating 150 cubiccentimeters of catalyst. The reactor was made of 316 stainless steel.

For each of the examples, the tubular reaction system was brought to thedesignated conditions. The EG and EDA were premixed to the appropriatefeed mole ratio and then pressure fed to the system. The liquid feed wasthen mixed with nitrogen (if used) and this mixture was passed to apreheater prior to entering the reaction zone.

The reaction mixture was passed through the reaction zone in a downflowfashion. The pressure in the reaction zone was controlled by a motorvalve at the outlet of the reactor. After leaving the reaction zone, thepressure of the stream was reduced from that of the reaction zone toslightly above atmospheric. This stream was then passed through a trapwhere the nitrogen (if used) was separated from the condensables whichwere collected in a semi-batch fashion. The condensable sample, whichcontains unreacted EG and EDA and the products of the reaction, was thenanalyzed for water by a Karl-Fisher precedure and for organics (amines)by capillary gas chromatography.

The catalysts employed are identified as follows:

    ______________________________________                                        Designation                                                                             Composition    Physical Properties                                  ______________________________________                                        A         TiO.sub.2 (anatase)/WO.sub.3                                                                 Particle size: 1/16 inch                                       TiO.sub.2 /WO.sub.3 wt.                                                                      cylindrical extrudates.                                        ratio = 80/20                                                       B         TiO.sub.2 (anatase)/WO.sub.3                                                                 Particle size: 1/8 inch                                        TiO.sub.2 /WO.sub.3 wt.                                                                      cylindrical extrudates;                                        ratio = 80/20  Catalyst surface area:                                                        227.9 m.sup.2 /gm.                                   C         TiO.sub.2 (anatase)/WO.sub.3                                                                 Particle size: 1/16 inch                                       TiO.sub.2 /WO.sub.3 wt.                                                                      cylindrical extrudates;                                        ratio = 80/20  Catalyst surface area:                                                        166.3 m.sup.2 /gm.                                   D         TiO.sub.2 (anatase)/                                                                         Particle size: 1/16 inch                                       AB1 (5.7 wt. % P)                                                                            cylindrical extrudates;                                                       Catalyst surface area:                                                        111.3 m.sup.2 /gm.                                   ______________________________________                                    

As used herein, ABl refers to a material obtained from Norton Company,Akron, Ohio, which is sodium trimetaphosphate and minor amounts ofsodium salts of orthophosphates and pyrophosphates.

The catalysts and/or supports employed in the examples hereinafter wereobtained from Norton Company, Akron, Ohio. Certain of the catalystsand/or supports were subsequently treated as follows:

Catalyst A preparation: Silicotungstic acid (18.0 grams) was dissolvedin distilled water (45 milliliters) and an aliquot sufficient to wet theTiO₂ /WO₃ support (55 grams) was used. After wetting, the catalyst wascalcined at a temperature of 350° C. for a period of 1 hour. Theimpregnation and calcination steps were repeated twice more to give thecatalyst.

                                      TABLE I                                     __________________________________________________________________________                  Example No.                                                                   1   2   3   4   5   6   7   8   9   10                          __________________________________________________________________________    Process Parameters                                                            Catalyst Type A   A   A   A   A   A   A   A   A   A                           Catalyst Weight, gm.                                                                        50  50  50  50  50  50  50  50  50  50                          Temperature, °C.                                                                     269.8                                                                             280 274.5                                                                             285 289.8                                                                             299.9                                                                             269.7                                                                             279.8                                                                             269.8                                                                             269.5                       Pressure, psig                                                                              614.7                                                                             614.7                                                                             614.7                                                                             614.7                                                                             614.7                                                                             614.7                                                                             614.7                                                                             614.7                                                                             614.7                                                                             614.7                       Time on Organics, hrs.                                                                      329.5                                                                             334 353.5                                                                             358 378 382 402 406 421.5                                                                             448                         EG SV, gmol/hr/kgcat                                                                        5.08                                                                              5.26                                                                              4.37                                                                              4.19                                                                              3.93                                                                              3.68                                                                              4.12                                                                              3.84                                                                              5.60                                                                              5.79                        EDA/EG mole ratio                                                                           2.95                                                                              2.95                                                                              2.95                                                                              2.95                                                                              2.95                                                                              2.95                                                                              2.95                                                                              2.95                                                                              2.95                                                                              2.95                        Crude Product Composition,                                                    wt. %                                                                         PIP           6.13                                                                              7.19                                                                              6.03                                                                              8.19                                                                              10.04                                                                             18.24                                                                             5.61                                                                              6.90                                                                              4.92                                                                              4.31                        AEEA          47.84                                                                             40.22                                                                             50.13                                                                             36.87                                                                             27.94                                                                             5.71                                                                              59.53                                                                             47.50                                                                             66.92                                                                             73.12                       AEP           2.39                                                                              4.45                                                                              2.86                                                                              6.09                                                                              8.14                                                                              20.40                                                                             2.01                                                                              3.48                                                                              1.24                                                                              0.00                        L-TETA        18.71                                                                             23.27                                                                             20.71                                                                             23.69                                                                             23.98                                                                             9.46                                                                              17.35                                                                             23.40                                                                             14.65                                                                             11.39                       Others        24.93                                                                             24.87                                                                             20.26                                                                             25.16                                                                             29.90                                                                             46.19                                                                             15.50                                                                             18.72                                                                             12.26                                                                             11.18                       Calculated Results                                                            EG Conversion, %                                                                            33.85                                                                             41.77                                                                             38.54                                                                             47.20                                                                             56.82                                                                             78.81                                                                             34.85                                                                             43.71                                                                             29.93                                                                             26.82                       EDA Conversion, %                                                                           11.10                                                                             18.13                                                                             16.71                                                                             24.42                                                                             24.79                                                                             31.46                                                                             14.03                                                                             19.71                                                                             10.80                                                                             10.30                       AEEA/PIP, weight ratio                                                                      7.80                                                                              5.60                                                                              8.31                                                                              4.50                                                                              2.78                                                                              0.31                                                                              10.61                                                                             6.88                                                                              13.61                                                                             16.95                       AEEA + L-TETA/PIP,                                                                          10.86                                                                             8.83                                                                              11.74                                                                             7.39                                                                              5.17                                                                              0.83                                                                              13.70                                                                             10.27                                                                             16.59                                                                             19.59                       weight ratio                                                                  __________________________________________________________________________

                                      TABLE II                                    __________________________________________________________________________                  Example No.                                                                   11  12  13  14  15  16  17  18  19  20                          __________________________________________________________________________    Process Parameters                                                            Catalyst Type B   B   B   B   B   B   B   B   B   B                           Catalyst Weight, gm.                                                                        50  50  50  50  50  50  50  50  50  50                          Temperature, °C.                                                                     269.8                                                                             280.0                                                                             274.5                                                                             285.0                                                                             289.8                                                                             299.9                                                                             269.7                                                                             279.8                                                                             269.8                                                                             269.5                       Pressure, psig                                                                              614.7                                                                             614.7                                                                             614.7                                                                             614.7                                                                             614.7                                                                             614.7                                                                             614.7                                                                             614.7                                                                             614.7                                                                             614.7                       Time on Organics, hrs.                                                                      329.5                                                                             334 353.5                                                                             358 378 382 402 406 421.5                                                                             448                         EG SV, gmol/hr/kgcat                                                                        4.68                                                                              4.96                                                                              4.39                                                                              4.26                                                                              4.11                                                                              3.83                                                                              3.82                                                                              3.75                                                                              5.37                                                                              5.46                        EDA/EG mole ratio                                                                           2.95                                                                              2.95                                                                              2.95                                                                              2.95                                                                              2.95                                                                              2.95                                                                              2.95                                                                              2.95                                                                              2.95                                                                              2.95                        Crude Product Composition,                                                    wt. %                                                                         PIP           4.60                                                                              5.56                                                                              4.77                                                                              6.58                                                                              8.07                                                                              12.41                                                                             4.73                                                                              5.89                                                                              4.29                                                                              3.92                        AEEA          62.46                                                                             53.02                                                                             62.35                                                                             46.63                                                                             36.30                                                                             12.02                                                                             66.84                                                                             54.58                                                                             74.00                                                                             73.68                       AEP           1.08                                                                              1.31                                                                              1.34                                                                              1.89                                                                              2.89                                                                              8.76                                                                              1.23                                                                              0.82                                                                              0.96                                                                              0.91                        L-TETA        16.45                                                                             23.64                                                                             19.16                                                                             27.74                                                                             30.65                                                                             26.02                                                                             17.38                                                                             24.25                                                                             14.36                                                                             13.12                       Others        15.41                                                                             16.47                                                                             12.39                                                                             17.16                                                                             22.09                                                                             40.79                                                                             9.82                                                                              14.47                                                                             6.40                                                                              8.36                        Calculated Results                                                            EG Conversion, %                                                                            42.99                                                                             54.71                                                                             47.28                                                                             64.06                                                                             73.55                                                                             91.66                                                                             44.13                                                                             55.63                                                                             40.32                                                                             37.22                       EDA Conversion, %                                                                           10.01                                                                             15.81                                                                             15.07                                                                             21.82                                                                             22.36                                                                             23.58                                                                             14.46                                                                             18.17                                                                             14.09                                                                             11.60                       AEEA/PIP, weight ratio                                                                      13.59                                                                             9.53                                                                              13.08                                                                             7.09                                                                              4.50                                                                              0.97                                                                              14.14                                                                             9.27                                                                              17.26                                                                             18.79                       AEEA + L-TETA/PIP,                                                                          17.17                                                                             13.78                                                                             17.11                                                                             11.30                                                                             8.30                                                                              3.07                                                                              17.82                                                                             13.39                                                                             20.61                                                                             22.13                       weight ratio                                                                  __________________________________________________________________________

                                      TABLE III                                   __________________________________________________________________________                  Example No.                                                                   21  22  23  24  25  26  27  28  29  30                          __________________________________________________________________________    Process Parameters                                                            Catalyst Type C   C   C   C   C   C   C   C   C   C                           Catalyst Weight, gm.                                                                        50  50  50  50  50  50  50  50  50  50                          Temperature, °C.                                                                     269.8                                                                             280 274.5                                                                             285 289.8                                                                             299.9                                                                             269.7                                                                             279.8                                                                             269.8                                                                             269.5                       Pressure, psig                                                                              614.7                                                                             614.7                                                                             614.7                                                                             614.7                                                                             614.7                                                                             614.7                                                                             614.7                                                                             614.7                                                                             614.7                                                                             614.7                       Time on Organics, hrs.                                                                      329.5                                                                             334 353.5                                                                             358 378 382 402 406 421.5                                                                             448                         EG SV, gmol/hr/kgcat                                                                        4.19                                                                              4.42                                                                              4.14                                                                              4.08                                                                              3.64                                                                              3.51                                                                              3.69                                                                              3.68                                                                              4.82                                                                              4.76                        EDA/EG mole ratio                                                                           2.95                                                                              2.95                                                                              2.95                                                                              2.95                                                                              2.95                                                                              2.95                                                                              2.95                                                                              2.95                                                                              2.95                                                                              2.95                        Crude Product Composition,                                                    wt. %                                                                         PIP           4.59                                                                              5.67                                                                              4.98                                                                              5.91                                                                              7.62                                                                              11.61                                                                             4.41                                                                              5.44                                                                              4.43                                                                              4.00                        AEEA          62.90                                                                             55.93                                                                             66.04                                                                             50.60                                                                             43.97                                                                             19.65                                                                             68.14                                                                             58.96                                                                             70.46                                                                             74.57                       AEP           1.13                                                                              1.40                                                                              1.32                                                                              1.89                                                                              2.63                                                                              7.14                                                                              0.79                                                                              0.55                                                                              0.72                                                                              0.93                        L-TETA        14.91                                                                             19.19                                                                             16.21                                                                             23.30                                                                             24.67                                                                             24.10                                                                             14.71                                                                             20.30                                                                             13.83                                                                             11.71                       Others        16.46                                                                             17.81                                                                             11.45                                                                             18.29                                                                             21.12                                                                             37.51                                                                             11.95                                                                             14.75                                                                             10.56                                                                             8.78                        Calculated Results                                                            EG Conversion, %                                                                            36.7                                                                              45.9                                                                              39.3                                                                              52.6                                                                              62.1                                                                              83.0                                                                              41.3                                                                              49.7                                                                              37.7                                                                              34.6                        EDA Conversion, %                                                                           8.5 13.0                                                                              11.7                                                                              18.6                                                                              15.6                                                                              18.7                                                                              13.9                                                                              16.0                                                                              12.9                                                                              10.8                        AEEA/PIP, weight ratio                                                                      13.7                                                                              9.9 13.3                                                                              8.6 5.8 1.7 15.5                                                                              10.8                                                                              15.9                                                                              18.6                        AEEA + L-TETA/PIP,                                                                          16.95                                                                             13.24                                                                             16.52                                                                             12.50                                                                             9.01                                                                              3.77                                                                              18.79                                                                             14.58                                                                             19.02                                                                             21.56                       weight ratio                                                                  __________________________________________________________________________

                                      TABLE IV                                    __________________________________________________________________________                  Example No.                                                                   31  32  33  34  35  36  37  38  39                              __________________________________________________________________________    Process Parameters                                                            Catalyst Type D   D   D   D   D   D   D   D   D                               Catalyst Weight, gm.                                                                        19.1                                                                              19.1                                                                              19.1                                                                              19.1                                                                              19.1                                                                              19.1                                                                              19.1                                                                              19.1                                                                              19.1                            Temperature, °C.                                                                     300 300 300 300 310 290 320 310 320                             Pressure, psig                                                                              614.7                                                                             614.7                                                                             614.7                                                                             614.7                                                                             614.7                                                                             614.7                                                                             614.7                                                                             614.7                                                                             614.7                           Time on Organics, hrs.                                                                      25  49  54  72.5                                                                              78  96  102 119.6                                                                             126                             EG SV, gmol/hr/kgcat                                                                        6.73                                                                              6.52                                                                              12.86                                                                             14.89                                                                             14.91                                                                             13.69                                                                             14.85                                                                             12.46                                                                             13.15                           EDA/EG mole ratio                                                                           3.00                                                                              3.00                                                                              3.00                                                                              3.00                                                                              3.00                                                                              3.00                                                                              3.00                                                                              3.00                                                                              3.00                            Crude Product Composition,                                                    wt. %                                                                         PIP           17.98                                                                             12.83                                                                             8.83                                                                              8.14                                                                              9.67                                                                              6.52                                                                              14.88                                                                             9.53                                                                              15.17                           AEEA          14.10                                                                             29.49                                                                             50.62                                                                             60.12                                                                             46.92                                                                             76.60                                                                             26.11                                                                             52.30                                                                             25.90                           AEP           6.79                                                                              2.55                                                                              1.44                                                                              1.38                                                                              2.16                                                                              0.00                                                                              2.71                                                                              2.43                                                                              2.90                            L-TETA        38.68                                                                             41.49                                                                             32.43                                                                             24.76                                                                             32.53                                                                             13.85                                                                             34.29                                                                             26.62                                                                             32.50                           Others        22.45                                                                             13.65                                                                             6.67                                                                              5.59                                                                              8.71                                                                              3.03                                                                              22.02                                                                             9.12                                                                              23.53                           Calculated Results                                                            EG Conversion, %                                                                            61.0                                                                              61.5                                                                              47.3                                                                              43.2                                                                              53.3                                                                              33.9                                                                              65.5                                                                              52.8                                                                              63.9                            EDA Conversion, %                                                                           13.6                                                                              18.2                                                                              10.2                                                                              7.4 10.5                                                                              4.3 7.5 9.7 7.1                             AEEA/PIP, weight ratio                                                                      0.8 2.3 5.7 7.4 4.9 11.8                                                                              1.8 5.5 1.7                             AEEA + L-TETA/PIP,                                                                          2.93                                                                              5.53                                                                              9.40                                                                              10.43                                                                             8.22                                                                              13.87                                                                             4.06                                                                              8.28                                                                              3.85                            weight ratio                                                                  __________________________________________________________________________

Although the invention has been illustrated by certain of the precedingexamples, it is not to be construed as being limited thereby; butrather, the invention encompasses the generic area as hereinbeforedisclosed. Various modifications and embodiments can be made withoutdeparting from the spirit and scope thereof.

We claim:
 1. A process for making linear triethylenetetramine andaminoethylethanolamine comprising condensing, in the absence of hydrogenas a reactant, ethylenediamine and ethylene glycol under condensationconditions including the presence of a catalytically effective amount ofa condensation catalyst selected from the group consisting of ametatungstate or mixtures thereof with one or more Group IV B metaloxides, wherein the ethylenediamine to ethylene glycol feed mole ratiois sufficient to provide under condensation conditions as aminesproduct, based on 100 percent of the weight of the amines product andexclusive of any water and/or ammonia and/or feed present,(a) greaterthan about 10.0 weight percent of L-TETA, (b) greater than about 10.0weight percent of AEEA, (c) less than about 20.0 weight percent of thecombination of PIP and AEP, (d) less than about 30.0 weight percent ofothers, (e) an AEEA to L-TETA weight ratio of less than about 5.0, and(f) a L-TETA+AEEA to PIP weight ratio of greater than about 5.0.
 2. Theprocess of claim 1 wherein the Group IVB metal oxide comprises a highsurface area titanium oxide or zirconium oxide.
 3. The process of claim1 wherein the condensation catalyst has a surface area greater thanabout 70 m² /gm.
 4. The process of claim 2 wherein the titanium oxidecomprises titanium dioxide and the zirconium oxide comprises zirconiumdioxide.
 5. The process of claim 1 wherein the Group IVB metal oxidecomprises a mixture of titanium oxide and zirconium oxide.
 6. Theprocess of claim 5 wherein the mixture of titanium oxide and zirconiumoxide comprises titanium dioxide and zirconium dioxide.
 7. The processof claim 2 wherein the condensation catalyst has a surface area greaterthan about 140 m² /gm.
 8. The process of claim 2 wherein thecondensation catalyst has a surface area greater than about 70 m² /gm.9. The process of claim 1 wherein the Group IVB metal oxide comprisesfrom about 25 weight percent to about 90 weight percent of the weight ofthe catalyst.
 10. The process of claim 1 wherein the Group IVB metaloxide comprises from about 50 weight percent to about 90 weight percentof the weight of the catalyst.
 11. The process of claim 1 wherein theGroup IVB metal oxide comprises from about 75 weight percent to about 90weight percent of the weight of the catalyst.
 12. The process of claim 1wherein the condensation catalyst is associated with a support material.13. The process of claim 12 wherein the support comprises an aluminamaterial or an alumina-silica material.
 14. The process of claim 12wherein the support comprises a silica material or a silica-aluminamaterial.
 15. The process of claim 12 wherein the support comprises fromabout 2 to about 50 percent by weight of the condensation catalyst. 16.The process of claim 1 wherein the ethylenediamine and ethylene glycolare condensed in the presence of ammonia.
 17. The process of claim 1wherein the amines product has a L-TETA yield weight percent of greaterthan about 20.0 and an AEEA yield weight percent of greater than about20.0, based on 100 percent of the weight of the product and exclusive ofany water and/or ammonia and/or feed present.
 18. The process of claim 1which is conducted at a temperature of from about 125° C. to about 400°C.
 19. The process of claim 1 which is conducted at a pressure of fromabout 50 psig to about 3000 psig.
 20. The process of claim 1 which iseffected in the liquid or vapor or supercritical liquid states.